JP5651107B2 - Copolymerization of olefins using transition metal initiators and polar comonomers supported on ketone diimine ligands for olefin homopolymerization - Google Patents

Description

CROSS REFERENCE TO RELATED APPLICATIONS This application claims the benefit of the earlier application filed May 19, 2008, application number 61 / 128,174, which is hereby incorporated by reference.

  This application relates generally to polymers, and more particularly to organometallic initiators that allow the polymerization and copolymerization of olefins.

  There is an uninterrupted interest in metal-mediated olefin polymerization in academic and industrial research facilities. In recent years, along with insights from mechanistic and theoretical studies, advances in steric control and improved functional group tolerance have greatly improved control over the final polymer structure and thereby the bulk properties of the resulting material. (1, 2, 3, 4, 5, 6, 7).

  Tuning the bulk properties of polyolefins through synthesis control is still the main focus of many industrial and academic research groups. These efforts have created advances in catalyst design from heterogeneous catalysts to “single site” systems, where the reaction of the “single site” system selects the ligand environment around the active metal center. (1,2,3,4,5,6,7). In this development, novel structures based on electrophilic, early transition metal catalysts play an important role, along with promoting activity and improving mechanistic understanding with cocatalysts. Examples showing how the metal center creates properties by controlling monomer insertion include propylene stereospecific polymerization (8, 9, 10, 11, 12, 13, 14), and ethylene and 1-alkene. Copolymerization (15, 16, 17, 18).

  In recent years, there has been a renewed interest in the design of late transition metal initiators due to their low oxyphilicity and resistance to inactivation by polar functional groups compared to their counterparts in early period metals (19, 20 21, 22, 23). Decreasing the sensitivity of such late metals to polar impurities allows polymerization under less severe conditions and also allows copolymerization with polar comonomers (24, 25, 26, 27). 28). Nickel and palladium based catalysts participate in chain walking reactions (29, 30, 31), allow polar functional groups (24, 25, 26, 27, 28), used in water (32, 33, 34) have been shown. These catalytic properties are of great interest for the development of materials with unique properties and for the development of new commercial processes.

  According to Brookhart et al., The introduction of cationic Pd (II) and Ni (II) based catalysts that convert ethylene and α-olefins into high molecular weight polymers led to the polymerization of ethylene using late metal catalysts. The area has been restored (1, 2, 3, 4, 5, 6, 7, 19, 20). High electrophilic metal centers and steric bulk in the ligand are important features for the production of high molecular weight polymers. The electrophilicity of the late metal center makes olefin insertion rapid and the use of bulk favors insertion in chain transfer. Changes in the backbone and aryl substituents allow control over steric and electronic effects at the metal center in the ligand.

  The copper (II) and zinc (II) complex supported by the β-diimine ligand is oxidatively decomposed to produce a ketone diimine derivative under aerobic conditions (Yokota et al.) (44).

  Recent literature shows current interest in living polymerization of olefins using transition metals. These reactions allow the synthesis of polyolefins with higher dimensional structure and improved physical properties (47, 48). Compared to early transition metal catalysts, late metal systems are more tolerant to functional groups (49, 20, 21, 50) and participate in “chain walk” reactions (3 , 30, 51, 52, 53) In such a chain walking reaction, the metal center moves along the growth of the polymer chain by a series of β-hydrogen desorption and reinsertion steps. Polymerization of ethylene with a late metal catalyst system produces polyethylene (PE) with various branches. Similarly, the “ethylene” chain results from linearization of higher α-olefins (3, 30, 51, 52, 53). These distinct features combined with living behavior make it possible to use elastomeric multi-block poly (α-olefin) (54), ethylene-propylene copolymer (18), regio block copolymer (18, 55, 56) and terminal This leads to the generation of new materials, such as amorphous PE (24) functionalized with.

  Currently, there are no late metal systems that allow the production of semi-crystalline PE directly from ethylene under living conditions. Accordingly, novel ligand metal binding or initiators are provided. In activity with various cocatalysts, the initiator polymerizes ethylene and propylene, and / or other olefin monomers into high molecular weight polymers. In addition, copolymerization of olefins with functionalized comonomers can be carried out. In some embodiments, the polymerization can be performed in a living behavior.

  Typical initiator structures include late transition metals with neutral chelating ligands containing Lewis basic functional groups.

In one aspect, a common initiator structure comprises the following formula (I):

  here,

  R, R ′, R ″ and R ′ ″ are each independently an achiral or chiral alkyl or aryl group, which may or may not have one or more functional groups. Often;

  M is Fe, Co, Ni, Pd or Pt;

  X is an alkyl, hydride or halogen group; and

L is O, N—R ″ ″, S or ═CH ₂ , where R ″ ″ is an alkyl or aryl group.

  Various embodiments are provided, in which R and R ′ are each alkyl, R ″ and R ′ ″ are each aryl; in embodiments, L is O; L is O, R and R ′ are each alkyl, R ″ and R ′ ″ are each aryl; in embodiments, R and R ′ are methyl, R ″ and R ′ ″, respectively. Also includes embodiments wherein each is aryl and L is O; embodiments include R and R ′ are each alkyl, R ″ and R ′ ″ are each 2,6 disubstituted aryl, Also includes embodiments in which L is O; and the initiator is 2,4-bis (2,6-diisopropylphenylimino) pentan-3-onedibromonickel or 2,4-bis (2-isopropyl-6) -Methylpheny (Ruimino) pentane-3-one dibromonickel.

In another aspect, a process for producing an organometallic initiator complex is provided, the process comprising mixing a metal compound with a ligand of the following formula (II):

Here, R, R ′, R ″ and R ′ ″ are each independently an achiral or chiral alkyl or aryl group, which may have one or more functional groups. L may be O, N—R ″ ″, S or ═CH ₂ , where R ″ ″ is an alkyl or aryl group.

  Various embodiments are provided, in which R and R ′ are each alkyl, R ″ and R ′ ″ are each aryl; in embodiments, L is O; L is O, R and R ′ are each alkyl, R ″ and R ′ ″ are each aryl; in embodiments, R and R ′ are methyl, R ″ and R ′ ″, respectively. Also include embodiments wherein each is aryl and L is O; embodiments include R and R ′ are each alkyl, R ″ and R ′ ″ are each 2,6 disubstituted aryl, Also includes embodiments in which L is O; embodiments include that R ″ and R ′ ″ are 2,6-diisopropylphenyl or 2-isopropyl-6-methylphenyl, respectively.

In some embodiments, the process for producing the organometallic complex utilizes a metal halide complex as the metal compound, and in one embodiment, the metal halide complex comprises (1,2-dimethoxyethane). ) NiBr ₂ complex.

In a further aspect, a polymerization step is provided. The process includes mixing one or more olefins with the organometallic complex to produce a polymer comprising the one or more olefins . In this step, the organometallic composite has the structure of formula (I) or any embodiment of formula (I). Various embodiments are provided, in which R and R ′ are each alkyl, R ″ and R ′ ″ are each aryl; in embodiments, L is O; L is O, R and R ′ are each alkyl, R ″ and R ′ ″ are each aryl; in embodiments, R and R ′ are methyl, R ″ and R ′ ″, respectively. Also includes embodiments wherein each is aryl and L is O; embodiments include R and R ′ are each alkyl, R ″ and R ′ ″ are each 2,6 disubstituted aryl, Also includes embodiments in which L is O; and in embodiments, the organometallic complex is 2,4-bis (2,6-diisopropylphenylimino) pentan-3-onedibromonickel, or 2,4- Bis (2-isopropyl-6-methylphenylimi B) pentane-3-one dibromonickel.

In various embodiments, the polymerization process utilizes one or more olefins, each of which is independently: R ¹ CH═CH ₂ ; cyclopentene; styrene; norbornene; one or more functionalities. Cyclopentene, styrene or norbornene substituted with a group; or a polar olefin of formula H ₂ C═CR ² X; where R ¹ is substituted with hydrogen, an alkyl group, or one or more functional groups Any of the alkyl groups, R ² is hydrogen, an alkyl group, an aryl group or an alkoxy group, and X is a polar group. Examples of X include, but are not limited to, Cl, halogen such as Br or _{F; -CN; -C 6 H 5} N; -CONR 3 R 4; -OR 3; -COOR 3; -OCOR 3; -COR ³ ; —C ₆ H ₅ OR ³ ; and / or —C ₆ H ₅ NR ³ R ⁴ ; wherein R ³ and R ⁴ are each independently hydrogen or an alkyl group, It may be C ₁ ~ ₁₂ alkyl group.

Preferred embodiments include those where the polar olefin can be H ₂ C═CH (CH ₂ ) _n CO ₂ R ⁵ , where R ⁵ is hydrogen or an alkyl group, and n is from 0 Between 20.

  In some embodiments, the polymerization process utilizes a single olefin, such as any of the olefins described herein, which results in a single polymerization. In other embodiments, the polymerization process utilizes two or more different olefins, including at least one or any combination of the olefins described herein, whereby the copolymerization is accomplished. .

  The polymerization process is performed under living polymerization conditions such that the polymer is produced by the living polymerization process. In such embodiments, the block copolymer is made by using two, three or more different monomers, wherein the monomers are at least one or any combination of the olefins described herein. Can be included.

  Furthermore, in one aspect of the polymerization process, a cocatalyst is used. The cocatalyst can be added to any embodiment in the polymerization process and can be an alkylaluminum, aluminoxane or borate compound.

  In various embodiments, the polymerization product produced by the polymerization process comprises a semicrystalline polymer.

  For a more complete understanding of the present invention, reference is made to the following description, taken in conjunction with the accompanying drawings, in which:

FIG. 1 is an ORTEP diagram of initiator 1 at a 50% probability level. FIG. 2 is a graph of the IR spectrum of a copolymer showing the incorporation of methyl acrylate into polyethylene. FIG. 3 is a graph showing optimization of the cocatalyst with initiator in the polymerization experiment. FIG. 4 is a table showing large scale polymerization of ethylene with initiator 1. FIG. 5 is a table showing large-scale copolymerization of ethylene and acrylate with initiator 1. FIG. 6 is a table showing large scale copolymerization of ethylene and 1-hexene. FIG. 7 is a differential scanning calorimetry trace of semicrystalline polypropylene. FIG. 8A shows the synthesis of polyethylene (PE), polypropylene (PP) and poly (1-hexene) using initiator 1 at low temperature, with symmetrical GPC traces and polydispersity below 1.1. FIG. 8B is a graph showing GPC traces of various polymers. FIG. 9 shows a plot of M _n against time for various polymers.

  A novel organometallic initiator complex is provided, which is accompanied by polymerization of olefins or functionalized comonomers to produce high molecular weight polymers (≧ 5,000). Olefin copolymerization is possible.

In particular, these initiator complexes have the following formula (I):

Here, R, R ′, R ″ and R ′ ″ are each independently an achiral or chiral alkyl or aryl group, which may have one or more functional groups. M is Fe, Co, Ni or Pd; X is an alkyl, hydrogen or halogen group; L is O, N—R ″ ″, S or ═CH ₂ Where R ″ ″ is an alkyl or aryl group. In a preferred embodiment, the initiator is 2,4-bis (2,6-diisopropylphenylimino) pentane-3-one dibromonickel or 2,4-bis (2-isopropyl-6-methylphenylimino) pentane-3. -Ondibromonickel.

The term “alkyl” refers to branched or unbranched saturated hydrocarbyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl, etc., cyclopentyl, cyclohexyl, etc. Such a cycloalkyl group. In preferred embodiments, the alkyl group can be a C ₁ ~ ₃₀ or C ₁ ~ _20.

  The term “aryl” refers to an aromatic hydrocarbyl group comprising a single aromatic ring or a plurality of aromatic rings, wherein the plurality of aromatic rings are fused together, covalently linked, or methylene And is bonded to a common group such as a portion of ethylene. In some embodiments, the aryl group comprises one aromatic ring, such as, for example, phenyl, naphthyl, biphenyl, diphenyl ether, diphenylamine, benzophenone, or two fused or bonded aromatic rings. Including. In preferred embodiments, aryl groups containing several substituents have 4 to 50 carbon atoms, 4 to 40 carbon atoms, 4 to 30 carbon atoms, 4 to 20 carbon atoms, or 4 to 10 carbon atoms. Or more preferably 6 to 50 carbon atoms, 6 to 40 carbon atoms, 6 to 30 carbon atoms, 6 to 20 carbon atoms, or 6 to 10 carbon atoms. Can have.

  The term “alkoxy” refers to an alkyl group attached to a single terminal ether linkage; that is, an alkoxy group is represented as O-alkyl, where alkyl is defined as above.

  Alkyl or aryl groups can be substituted with functional groups. As used herein, the term “substituted” in association with a hydrocarbyl group refers to a hydrocarbyl group in which at least one hydrogen atom bonded to a carbon atom is replaced with one or more substituents. For example, a disubstituted aryl group such as a diisopropylphenyl group has two substituents replacing the two hydrogen atoms of the original aryl group. Substituents include, but are not limited to, “functional” such as halo, ester, keto (oxo), amino, imino, hydroxyl, carboxyl, phosphite, phosphonite, phosphine, phosphinite, thioether, amide, nitrile and ether. May be “functional” or “functional”. For example, methyl acrylate can be considered a hydrocarbyl substituted with a carboxyl functionality. In preferred embodiments, the alkyl or aryl group can have 1, 2, 3, 4 or more substituents.

  In the complex of formula (I), R, R ', R "and R" "can each independently be an achiral or chiral hydrocarbyl group. As is well known, the term “chiral” refers to a molecule that has the property of being unable to overlap a mirror image partner, and the term “achiral” refers to a molecule that can overlap a mirror image partner.

ここで、Ｒ、Ｒ’、Ｒ’’及びＲ’’’は、それぞれ独立してアキラルまたはキラルのアルキルまたはアリール基であり、これらは、１またはそれ以上の官能基を有していても有していなくてもよく、Ｌは、Ｏ、Ｎ−Ｒ’’’’、Ｓまたは＝ＣＨ₂であり、ここで、Ｒ’’’’は、アルキルまたはアリール基である。 Initiators can be prepared by binding a ligand to a suitable metal. In some embodiments, the initiator is prepared by a reaction sequence as shown in Example 1 (below). The general formula (II) of such a ligand is as follows:

Here, R, R ′, R ″ and R ′ ″ are each independently an achiral or chiral alkyl or aryl group, which may have one or more functional groups. L may be O, N—R ″ ″, S or ═CH ₂ , where R ″ ″ is an alkyl or aryl group.

The initiator according to the present invention is capable of polymerizing and / or copolymerizing one or more olefins, which olefins have: R ¹ CH═CH ₂ ; cyclopentene; styrene; one or more functional groups. A substituted cyclopentene, styrene or norbornene derivative having; or a polar olefin of formula H ₂ C═CR ² X; where R ¹ is hydrogen, an alkyl group, or an alkyl group substituted with one or more functional groups R ² is hydrogen, an alkyl group, an aryl group or an alkoxy group, and X is a polar group. In these embodiments, R ′ is hydrogen, alkyl, or one or more functional groups (eg, —OH, —NH ₂ , —CN, —COOR, —OCOR, —C (O) R, or —C (O ) NRR ′, wherein R and R ′ are each independently a substituted alkyl having a hydrogen or alkyl group). Examples of X include, but are not limited to,: Cl, halogen such as Br or _{F; -CN, -C 6 H 5} N, -CONR 3 R 4; -OR 3; -COOR 3; -OCOR 3; ^{_{-C 6 H 5 oR 3; -COR}} 3, and / or _{^{-C 6 H 5 NR 3 R 4}} ; wherein, R ³ and R ⁴ are each independently hydrogen or an alkyl group, the alkyl group It may be an alkyl group of C ₁ ~ _12. In addition, the polar olefin can be H ₂ C═CH (CH ₂ ) _n CO ₂ R ⁵ , where R ⁵ is hydrogen or an alkyl group and n is between 0 and 20. The polymers produced in connection with these initiators can exhibit a unique microstructure.

  Polymerization can occur at temperatures from -100 ° C or about -100 ° C to 250 ° C or about 250 ° C. A preferred range is from 60 ° C or about 60 ° C to 200 ° C or about 200 ° C. By using such polymerization conditions with ethylene or propylene, high molecular weight polymers having a unique structure can be produced (see Examples 2 and 3 below). In other embodiments, these initiators can be used for copolymerization with functionalized comonomers (see Example 4 below) or other 1-alkenes.

  Cocatalysts can be used with the above initiators for polymerization / copolymerization reactions. Such cocatalysts include, but are not limited to, any alkylaluminum, alkylaluminoxane and borate cocatalysts known in the art. Such cocatalysts include, but are not limited to, methylaluminoxane (MAO), modified methylaluminoxane type 3A, or trimethylaluminum (TMA).

In certain embodiments with the complex of initiator of formula (I), the polymerization can occur under conditions that result in a living polymerization process. In these embodiments, a single monomer can be polymerized in a living manner, or more than one monomer can undergo a living polymerization. By adjusting conditions such as temperature and pressure, living polymerization occurs so that the growth of M _n as a function of time in the polymer is linear. Under living conditions, a polymer having a symmetric molecular weight distribution and a PDI value of 1.3 or less can be obtained.

  By using living conditions, block copolymers including diblock, triblock and other multiblock copolymers can be prepared. For example, under living polymerization conditions, a first monomer can be polymerized to produce a polymer product, and a second monomer can be added to the polymer to produce a block comonomer. In addition, tapered, regioblock, and / or end-functionalized polymers can be prepared.

  Polymerization under living conditions can also produce semicrystalline polymers such as semicrystalline polyethylene or polypropylene. The term “semicrystalline” refers to a polymer having both crystalline and amorphous portions. Polymerization under living conditions can also produce amorphous polymers.

  The invention may be better understood by being described with examples, which are intended solely for the purpose of illustration and in any case the appended claims Should not be construed as limiting the scope of the invention defined in.

Example 1
Synthesis of initiator 1 2,4-bis (2,6-diisopropylimino) pentan-3-one dibromonickel (initiator 1)

Initiator 1 is synthesized from 2,4-bis (2,6-diisopropylphenylimino) pentan-3-one as a ligand. This ligand can be made according to the following reaction scheme and procedure.

[Cu ^II (1) (AcO)]. While stirring at room temperature to a solution containing Cu ^II (CH ₃ COO) ₂ —H ₂ O (2.38 g) in CH ₃ OH—CH ₂ Cl ₂ (v / v = 1: 1,500 mL), A solution containing 1 (5 g) in CH ₂ Cl ₂ (20 mL) was added dropwise. After the mixture was stirred overnight, the solvent was removed under vacuum. The resulting brown material was dissolved in CH ₂ Cl ₂ (100 mL) and extracted three times with water (100 mL × 3). The solvent was removed under vacuum and the brown solid was washed with water, collected by filtration on a fritted funnel and dried overnight under high vacuum (5.5 g, 84.9%).

[Cu ^II (1) AcO] (5 g) was treated at 50 ° C. in methanol (1000 mL) in a reflux condenser fitted with two septum-capped three-necked round bottom flasks and oil bubblers. . The solution was bubbled with oxygen vigorously for 72 hours or until a complete color change from brown to purple was observed. At this point, oxygen was bubbled for another 12 hours and the volume was reduced to 100 mL by bubbling oxygen at 50 ° C. The methanol solution was cooled by allowing it to stand at room temperature overnight under an oxygen atmosphere. Purple crystals were collected by filtration. 2,4-Bis (2,6-diisopropylphenylimino) pentan-3-one (3 g, 75.2%) was isolated by treating the purple crystals with NH ₃ water. Removal of the solvent gave a pale yellow solid.

開始剤１の結晶構造 Initiator 1 was synthesized according to Reaction Scheme 1 under an inert atmosphere. Prior to use, all ligands were dried by various methods. While stirring a suspension containing (1,2-dimethoxyethane) NiBr ₂ complex (71.1 mg, 0.231 mmol) in 15 mL of methylene chloride, the suspension was added to 5 mL of methylene chloride. The contained 2,4-bis (2,6-diisopropylphenylimino) pentan-3-one (100 mg, 0.231 mmol) was added in one portion at room temperature. Shortly after the addition of the ligand, the solution began to turn red. The suspension was stirred for an additional 2.5 hours at room temperature. The reaction mixture was then filtered through celite and the solvent was removed under vacuum. The red powder was washed with cooled diethyl ether (−35 ° C., 3 × 10 mL), dried, resuspended in methylene chloride (10 mL), filtered again through Celite, and dried. A pure water compound as a red powder was obtained with a yield of 49.0% (73.7 mg, 0.113 mmol). Anal. Calc. (C ₂₉ H ₄₀ N ₂ ) C, 53.49; H, 6.19; N, 4.30. Found: C, 53.71; H, 6.24; N, 4.23.

Crystal structure of initiator 1

Single crystals were obtained from the concentrated solution in methylene chloride at -35 ° C. Its molecular binding was consistent with the N, N-coordination structure where the ligand is bound as a neutral donor. The bond distance within the six-membered chelate ring is consistent with the structure shown in Scheme 1, as shown by the selected bond length (A) below, which is: C ( 4) -N (2) 1.291, C (3) -C (4) 1.518, C (2) -N (1) 1.288, C (2) -C (3) 1.511 and C (3) -O (1) 1.222. The Ni (II) atom adopts a quasi-tetrahedral coordination structure with ¹ H-NMR in which contact interaction occurs, which exhibits a relatively narrow line width at room temperature. The six-membered chelate ring adopts a boat-type conformation. See FIG. 1 as ORTEP showing initiator 1.
Example 2
Polymerization of ethylene

  Using initiator 1, single polymerization of ethylene was carried out by the following method. Initiator 1 contained in 90 mL toluene was charged into a glove box of a 300 mL steel autoclave reactor equipped with an additional funnel. Toluene was followed by methylaluminoxane (Aldrich, 10 wt% in toluene) (MAO) to an additional funnel so that the final volume was 10 mL. The reactor was sealed inside the glove box and an ethylene line was attached. The reactor was pre-pressurized with ethylene. The MAO solution was then charged under a predetermined ethylene pressure, where the MAO solution was continuously fed at that pressure over the course of the reaction. After a predetermined time, the ethylene was discharged and acidic methanol (10% HCl) was added to cool the polymerization. The precipitated polymer was collected by filtration, washed with copious amounts of methanol, subsequently washed with acetone, and dried overnight under high vacuum. The polymerization activity was calculated from the mass of the obtained product. At 135 ° C. in o-dichlorobenzene, the polymer was evaluated by GPC analysis in comparison to polystyrene standards (high temperature chromatograph, Pl-GPC 200 in the polymer laboratory). The melting point of the polymer was measured in 3 cycles at a rate of 10 ° C./min in a temperature range of 0-180 ° C. in a TA Instruments differential scanning calorimeter. The optimum amount of cocatalyst (MAO) was measured as shown in FIG. Table 1 shows the selected polymerization data.

Table 1 shows the relationship between temperature and activity. The activity increased dramatically with temperature, but only a limited rate of mass transfer was obtained above 40 ° C. The polymer exhibits a high molecular weight (> 1 × 10 ⁶ ) with a relatively short reaction time (calculated 10 minutes). The produced polymer has a melting point between 80 and 125 ° C.
Example 3
Polymerization of propylene

Using initiator 1, propylene single polymerization was carried out by the following method. Initiator 1 contained in 90 mL toluene was charged into a glove box of a 300 mL steel autoclave reactor equipped with an additional funnel. MAO (Aldrich, 10 wt% in toluene) was added to the additional funnel, followed by toluene, so that the final volume was 10 mL. The reactor was sealed inside the glove box and a propylene line was attached. The reactor was pre-pressurized with propylene. Then, MAO solution was charged under a predetermined propylene pressure, where the MAO solution was continuously fed at that pressure over the course of the reaction. After a predetermined time, the ethylene was discharged and acidic methanol (10% HCl) was added to cool the polymerization. The precipitated polymer was collected by filtration, washed with copious amounts of methanol, subsequently washed with acetone, and dried overnight under high vacuum. The polymerization activity was calculated from the mass of the obtained product. At 135 ° C. in o-dichlorobenzene, the polymer was evaluated by GPC analysis in comparison to polystyrene standards (high temperature chromatograph, Pl-GPC 200 in the polymer laboratory). Measure glass transition temperature (T _g ) and melting point (T _m ) in 3 cycles at a rate of 5 ° C./minute using a temperature scanning range of 70-180 ° C. in a differential scanning calorimeter (model DSC 2920) from TA Instruments did. A ¹³ C NMR spectrum of the polymer was obtained in 1,1,2,2-tetrachloroethane-d ₂ at room temperature. Table 2 (below) shows the selected polymerization data.

The produced polypropylene is mainly amorphous with a T _g in the range of -35 ° C to -20 ° C depending on the reaction temperature. As shown in Table 3 below, entries 1, 2 and 4 represent the following stereoregularity.

The essential difference in the microstructure of polypropylene produced at different temperatures is that these catalysts allow control of the microstructure in the final product by changes in temperature, pressure, monomer concentration and various other reaction conditions. Indicates that In addition, changes in the ligand are expected to provide further control and substantial stereoregularity. The melting points T _m = 150 ° C. and T _c = 117 ° C. in entry 3 indicate that the polypropylene obtained with initiator 1 exhibits some crystallinity.
Example 4
Copolymerization of ethylene and methyl acrylate

Using initiator 1, ethylene and methyl acrylate were copolymerized by the following method. Initiator 1 contained in 90 mL toluene was charged into a glove box of a 300 mL steel autoclave reactor equipped with an additional funnel. A predetermined amount of MAO (Aldrich, 10 wt% in toluene) was added to the additional funnel, followed by toluene, so that the final volume was 10 mL. The reactor was sealed inside the glove box and an ethylene line was attached. The reactor was pre-pressurized with ethylene. The MAO-methyl acrylate solution was then charged under a predetermined pressure of ethylene where the solution was fed at that pressure throughout the course of the reaction. After a predetermined time, ethylene was discharged and acidic methanol (10% HCl) was added to cool the polymerization. The precipitated polymer was collected by centrifugation, washed with copious amounts of methanol, followed by THF and dried overnight under high vacuum. The polymerization activity was calculated from the mass of the obtained product. At 135 ° C. in o-dichlorobenzene, the polymer was evaluated by GPC analysis in comparison to polystyrene standards (high temperature chromatograph, Pl-GPC 200 in the polymer laboratory). A ¹ H NMR spectrum of the polymer was obtained at 115 ° C. in 1,1,2,2-tetrachloroethane-d ₂ .

Addition of methyl acrylate to the reaction significantly reduced activity but produced random copolymers with low levels of linkage. It is expected to improve yield, activity, control and uptake by better control of the final product by changing reaction conditions and initiator structure. Entry 1 in Table 4 represents the characteristic (C = O) stretch in the IR spectrum, but no uptake was detected by ¹ H NMR. Uptake is higher with decreasing ethylene pressure and increasing methyl acrylate concentration (entry 2). FIG. 2 shows the IR spectra of entries 1 and 2.
Example 5
Large-scale copolymerization of ethylene using initiator 1

  Using initiator 1, single polymerization of ethylene was carried out by the following method. A 2000 mL steel autoclave reactor equipped with an additional straw was heated in an oven at 150 ° C. overnight. The reactor was assembled and heated and purged with nitrogen a total of 3 times and evacuated. The reactor was then sealed under nitrogen. Predetermined amounts of solution and cocatalyst were added using standard Schlenk and air-free techniques. An initiator stock solution was prepared and added to the addition straw under a stream of nitrogen. The reactor was sealed and an ethylene line was attached. The reactor was pre-pressurized with ethylene. Then, an initiator solution was charged under a predetermined ethylene pressure, where the initiator solution was continuously fed at that pressure over the course of the reaction. 10 mL of ethanol was added to cool the polymerization. The precipitated polymer was collected by filtration and washed with copious amounts of acidic methanol (10% HCl); then washed with methanol followed by acetone and dried in a vacuum oven overnight. The polymerization activity was calculated from the mass of the obtained product. At 135 ° C. in o-dichlorobenzene, the polymer was evaluated by GPC analysis in comparison to polystyrene standards (high temperature chromatograph, Pl-GPC 200 in the polymer laboratory). In a differential scanning calorimeter (model DSC 2920) from TA Instruments, the melting point of the polymer was measured in 3 cycles at a rate of 10 ° C./min using a temperature range of 0 to 180 ° C.

  FIG. 4 shows selected polymerization data obtained from a single polymerization of ethylene and shows the following: Ethylene consumption is consistent over a 30 minute process. When MMAO is used as a cocatalyst, the activity is remarkably higher than that of MAO.

The activity increased significantly with temperature to 22800 kg P / mol Ni hr at 50 ° C. (Reaction 17). Ethylene consumption is consistent for 30 minutes at 75 ° C. (Reaction 11), indicating that the catalytic properties are robust to decomposition with increasing temperature. In addition, the catalytic properties are highly active in the presence of H ₂ (reaction 13). The melt flow rate of the polymer obtained in reaction 13 suggests that H ₂ acts as a chain transfer agent.
Example 6
Large scale copolymerization of ethylene and acrylate with initiator (1)

Using initiator 1, copolymerization of ethylene and methyl or t-butyl acrylate was carried out by the following method. The oven in a 2000 mL steel autoclave reactor equipped with an additional straw was heated at 150 ° C. overnight. The reactor was assembled and heated and purged with nitrogen a total of 3 times and evacuated. The reactor was then sealed under nitrogen. Predetermined amounts of solution, cocatalyst and acrylate were added using standard Schlenk and air-free techniques. Acrylic acid ester was added to reactions 14 and 15 to make a 0.082M solution. An initiator stock solution was prepared and added to an additional straw. The reactor was sealed and an ethylene line was attached. The reactor was pre-pressurized with ethylene. Then, an initiator solution was charged under a predetermined ethylene pressure, where the initiator solution was continuously fed at that pressure over the course of the reaction. 10 mL of ethanol was added to cool the polymerization. The precipitated polymer was collected by filtration and washed with copious amounts of acidic methanol (10% HCl); then washed with methanol followed by acetone and dried in a vacuum oven overnight. The polymerization activity was calculated from the mass of the obtained product. At 135 ° C. in o-dichlorobenzene, the polymer was evaluated by GPC analysis in comparison to polystyrene standards (high temperature chromatograph, Pl-GPC 200 in the polymer laboratory). ¹ H and ¹³ C NMR spectra of the polymer were obtained in 1,1,2,2-tetrachloroethane-d ₂ at 115 ° C.

FIG. 5 shows the results of copolymerization using ethylene and acrylic acid ester. The figure shows that the copolymerization of ethylene and methyl acrylate proceeds with good activity in the presence of MMAO at 50 ° C. and 3.0 MPag. The uptake of methyl acrylate in Reaction 14 was 0.14 mol%. Compared to small scale reactions, this shows that the choice of cocatalyst and reaction conditions is important for activity, uptake and polymer microstructure. Under the same conditions, the copolymerization of ethylene and tert-butyl acrylate shows lower activity and less uptake. Although no uptake was detected by NMR in Reaction 15, a peak corresponding to (C═O) stretching was observed in the IR spectrum of the copolymer produced.
Example 7
Large scale copolymerization of ethylene and 1-hexene with initiator (1)

Using initiator 1, ethylene and 1-hexene were copolymerized by the following method. A 2000 mL steel autoclave reactor equipped with an additional straw was heated in an oven at 150 ° C. overnight. The reactor was assembled and heated and purged with nitrogen a total of 3 times and evacuated. The reactor was then sealed under nitrogen. A predetermined amount of solution, cocatalyst and 50 mL of 1-hexene were added using standard Schlenk and air-free techniques. An initiator stock solution was prepared and added to an additional straw. The reactor was sealed and an ethylene line was attached. The reactor was pre-pressurized with ethylene. Then, an initiator solution was charged under a predetermined ethylene pressure, where the initiator solution was continuously fed at that pressure over the course of the reaction. 10 mL of ethanol was added to cool the polymerization. The precipitated polymer was collected by filtration and washed with copious amounts of acidic methanol (10% HCl); then washed with methanol followed by acetone and dried in a vacuum oven overnight. The polymerization activity was calculated from the mass of the obtained product. At 135 ° C. in o-dichlorobenzene, the polymer was evaluated by GPC analysis in comparison to polystyrene standards (high temperature chromatograph, Pl-GPC 200 in the polymer laboratory). ¹ H and ¹³ C NMR spectra of the polymer were obtained in 1,1,2,2-tetrachloroethane-d ₂ at 115 ° C.

The results of the above copolymerization reaction of ethylene and 1-hexene are shown in FIG. The figure shows that reaction 16 exhibits high activity consistent with an increase in rate in the copolymerization reaction. Temperature control was not maintained, but based on additional butyl and long chain branching, the 1-hexene incorporation was calculated to be 0.32 mol%. This indicates that ethylene and 1-hexene can be copolymerized with high activity.
Example 8
Synthesis of 2,4-bis (2-isopropyl 6-methylphenylimino) pentan-3-one dibromonickel (Initiator 2)

例９
開始剤２を伴ったエチレンの重合 Initiator 2 was synthesized according to Reaction Scheme 2 under an inert atmosphere. Prior to use, all ligands were dried by various methods. While stirring a suspension containing (1,2-dimethoxyethane) NiBr2 complex (82.0 mg, 0.266 mmol) in 15 mL of methylene chloride, the suspension was contained in 5 mL of methylene chloride. 2,4-Bis (2-isopropyl-6-methylphenylimino) pentan-3-one (100 mg, 0.266 mmol) was added in one portion at room temperature. Shortly after the addition of the ligand, the solution began to turn red. The suspension was stirred for an additional 2.5 hours at room temperature. The reaction mixture was then filtered through celite and the solvent was removed under vacuum. The red powder was washed with cooled diethyl ether (−35 ° C., 3 × 10 mL), dried, resuspended in methylene chloride (10 mL), filtered again through Celite, and dried. A pure water compound as a red powder was obtained in a yield of 82.0% (130.0 mg, 0.218 mmol). Anal. CaIc. _{(C 25 H 32 N 2)} C, 50.46; H, 5.42; N, 4.71. Found: C, 52.38; H, 5.67; N, 4.80.

Example 9
Polymerization of ethylene with initiator 2

  Using initiator 2, single polymerization of ethylene was carried out by the following method. Initiator 2 contained in 90 mL of toluene was charged into a glove box of a 300 mL steel autoclave reactor equipped with an additional funnel. MAO (Aldrich, 10 wt% in toluene) was added to the additional funnel, followed by toluene, so that the final volume was 10 mL. The reactor was sealed inside the glove box and an ethylene line was attached. The reactor was pre-pressurized with ethylene. The MAO solution was then charged under a predetermined ethylene pressure, where the MAO solution was continuously fed at that pressure over the course of the reaction. After a predetermined time, the ethylene was discharged and acidic methanol (10% HCl) was added to cool the polymerization. The precipitated polymer was collected by filtration, washed with copious amounts of methanol, subsequently washed with acetone, and dried overnight under high vacuum. The polymerization activity was calculated from the mass of the obtained product. At 135 ° C. in o-dichlorobenzene, the polymer was evaluated by GPC analysis in comparison to polystyrene standards (high temperature chromatograph, Pl-GPC 200 in the polymer laboratory). The melting point of the polymer was measured in 3 cycles at a rate of 10 ° C./min in the temperature range of 0-180 ° C. in a TA Instruments differential scanning calorimeter (model DSC 2920). Table 5 below shows the selected polymerization data.

例１０
プロピレンの低温重合

Example 10
Low temperature polymerization of propylene

Using initiator 2, single polymerization of propylene was carried out by the following method. Initiator 2 contained in 90 mL of toluene was charged into a glove box of a 300 mL steel autoclave reactor equipped with an additional funnel. MAO (Aldrich, 10 wt% in toluene) was added to the additional funnel, followed by toluene, so that the final volume was 10 mL. The reactor was sealed inside the glove box and a propylene line was attached. Propylene was condensed at 0 ° C. for 5 minutes. The reactor was then cooled to the desired temperature and the MAO solution was charged. After a predetermined time, propylene was discharged and acidic methanol (10% HCl) was added to cool the polymerization. The precipitated polymer was collected by filtration, washed with copious amounts of methanol, subsequently washed with acetone, and dried overnight under high vacuum. The polymerization activity was calculated from the mass of the obtained product. At 135 ° C. in o-dichlorobenzene, the polymer was evaluated by GPC analysis in comparison to polystyrene standards (high temperature chromatograph, Pl-GPC 200 in the polymer laboratory). In a TA Instruments differential scanning calorimeter (model DSC 2920), the glass transition temperature (T _g ) and melting point (T _m ) were measured in 3 cycles at a rate of 5 ° C./min using a temperature range of −70 to 180 ° C. It was measured. Table 6 below shows the selected polymerization data.

FIG. 7 shows a graph created for entry 2 in Table 6 above by differential scanning calorimetry. The melting point (T _m ) and the corresponding crystallization temperature (T _c ) indicate the conversion from a pure amorphous polymer to a polymer with crystallinity based on ligand symmetry and reaction conditions. This indicates that the microstructure can be controlled based on the choice of ligand and the corresponding reaction conditions.
Example 11
Comparative example

The following comparative examples are included to show the importance of the ketone functional group in the ligand. Complex 5 (ArN = C- (Me) CH 2 C (Me) = NAR] NiBr 2, wherein, Ar = 2,6-diisopropylphenyl) (46), the main chain (in FIG. 1 C (3) ) Corresponding to the β-diimine complex of Ni (II) lacking the ketone functional group. Complex 5 is obtained in two important ways by a similar α-diimine complex (ie, [ArN = C- (Me) C (Me) = NAr] NiBr ₂ , where Ar = 2,6 diisopropylphenyl). A precursor for conducting ethylene polymerizations different from the catalyzed ethylene polymerization: the polyethylene produced is more linear and the complex 5 is a less active catalyst precursor. In the reported experiment, Complex 5 (52 mg, 0.080 mmol) was placed in a 100 mL autoclave reactor and ethylene was flushed. A solution containing modified methylaluminoxane in 240 mL of toluene (240 mL, Al with 64 wt% in toluene from Akzo, 4.88 mmol) was added under nitrogen. The reactor was pressurized with ethylene to 280 psi and stirred for 3.5 hours. At this time, the reaction temperature increased from 27 to 31 ° C., and 4.07 g of PE (Tm = 120.2 ° C.) was obtained. Molecular weight data is not included. This corresponds to an activity of 14.5 (kg P / mol Ni hr).

The complex ArN = C (Me) -C (Me) = at 25 ° C. by adding a standard catalyst solution (1.7 μmol catalyst) to a Schlenk flask containing 100 mL toluene and under 1 atm with ethylene. Polymerization of ethylene with NAr) NiBr ₂ (Ar = 2,6-diisopropyl) / MAO was carried out. The solution was brought to the desired temperature and a 10% solution containing MAO (˜1000 eq) in toluene was added. The solution was stirred for 15 minutes. Monomer began to precipitate in a few minutes. The polymerization was cooled and the polymer was precipitated with acetone. The obtained polymer was dried under vacuum to obtain 4.6 g of PE. M _w = 7.6 × 10 ⁻⁴ , M _n = 3.1 × 10 ⁻⁴ . Activity = 11000 kg PEmol ^-1 Ni hr ^-1 .
Living polymerization

Examples 12-15 relate to living polymerization reactions. Example 12 shows the results of the polymerization reaction, and Examples 13-15 provide information that supports the results shown in Example 12.
Example 12
Living polymerization using initiator 1

Starting with the aforementioned initiator 1 / MAO reactivity, the polydispersity (PDI) of the PE product was shown to decrease with decreasing reaction temperature (T _rxn ) (57). . To assess whether the active species can polymerize ethylene in a living manner, volatiles are removed from the commercially available MAO under vacuum until a free flowing white powder is obtained. did. This treatment is commonly used to remove free TMA that may be involved in the termination and strand conversion reactions (58). A series of polymerizations were performed to investigate the effect of T _rxn and ethylene pressure (P _C2H4 ). In these reactions, 40 mL of toluene and MAO were added to a 100 mL autoclave reactor so that [Al] / [Ni] = 250. A stock solution of initiator 1 was prepared and 1.5 μmol of initiator 1 contained in about 1 mL of CH ₂ Cl ₂ was added to the additional funnel. Polymerization was initiated by pre-pressurizing the reactor and additional funnel with ethylene, cooling to the appropriate temperature and charging the initiator (1) under rapid stirring conditions. The reaction was terminated by continuously feeding ethylene over the course of the polymerization and cooling with methanol or triethylsilane.

Table 7 summarizes the results of the initial screening studies. The comparison of entries 1 and 2, as measured by gel permeation chromatography (GPC) calibrated against polystyrene standards, shows that T C from 20 ° C. to 10 ° C. while keeping P _C2H4 constant at 300 psi. _It shows that PDI (1.60 vs. 1.35) is narrowed by decreasing _rxn . As shown in entry 3, by reducing P _C2H4 to 150 psi at T _rxn = 10 ° C., the PDI is further narrowed to 1.22. A PE PDI = 1.09 was obtained at T _rxn = -10 ° C, P _C2H4 = 150 psi (entry 4). When the polymerization was allowed to proceed for 20 minutes instead of 10 minutes under the same conditions, the molecular weight increased by approximately two factors (entry 4 vs. 5). Entry 6 has almost the same characteristics as those obtained with P _C2H4 = 150 psi (entry 4) for PDI, number average molecular weight (M _n ) and melting point (T _m ) by reducing P _C2H4 to 50 psi. This shows that a GPC peak having more symmetry than entry 4 (see Example 13, etc., below) can be obtained. The effect of the cooling agent and method is shown by comparing entry 6 (methanol) to entry 7 (triethylsilane). The data in Table 7 show that the product properties are not discernable, but the GPC trace after cooling with methanol contains a small shoulder of the high molecular weight product, which is after cooling with triethylsilane. can not see. For this reason, triethylsilane was utilized in a continuous reaction. Entry 8 shows that excellent control in molecular weight properties can be obtained after 60 minutes; the reaction equation and GPC trace for this product are shown in FIGS. 8A and 8B, respectively. This PE _exhibits a melting point (T _m ) of 122 ° C. and crystallinity (X _c ) of 32% despite the low ethylene pressure (P _CH2H4 = 50 psi).

  FIG. 8B shows PE, PP and PH GPC traces under the conditions of entries 8, 9 and 10 respectively in Table 7.

FIG. 9 shows a plot of M _n versus time under conditions similar to entry 7 (vs time using initiator 1 / MAO at −10 ° C. in PE, PP and PH as measured by GPC. _Mn (■) and PDI (x)). A linear increase in M _n as a function of time and a PDI value below 1.10 is consistent with the formation of semicrystalline PE under living conditions, with the results in Table 7. The initiator 1 / MAO compound can be used to polymerize propylene under living conditions. These reactions included condensing 5 mL of propylene into a 300 mL reactor charged with 100 mL of toluene and MAO so that [Al] / [Ni] = 250. The reaction was cooled to −10 ° C. and polymerization was initiated by the introduction of 10 μmol initiator 1. Entry 9 of Table 7 shows the results for PP obtained after 120 minutes of reaction; the GPC trace of this product is shown in FIG. 8B. An aliquot obtained over the course of the polymerization shows that M _n as a function of time is in a linear relationship, as shown in FIG. These characteristics, combined with a PDI value of less than 1.06, indicate that it is a living polymerization. A melting transition was observed at T _m = 59 ° C. and up to 9% crystallinity.

The reaction with 1-hexene was carried out with [1-hexene] = 0.85M under the same conditions as entry 9. The polymerization was sampled over the course of the reaction and product testing shows a linear increase in M _n with time and a low PDI value, as shown in FIG. Entry 10 of Table 7 contains the results for the polymer produced in 120 minutes; the GPC trace of this product is shown in FIG. 8B. DSC analysis shows that the polymer produced is amorphous (T _g = −62.0 ° C.).

The method described herein provides conditions that allow the living polymerization of ethylene and α-olefins by the use of initiator 1 / MAO. This is clearly the first late metal system that can polymerize ethylene in a living manner to obtain semi-crystalline PE as compared to the pseudo-living polymerization as in the Diamanti et al. (25) method. This excellent control surprisingly gives the fact that PE precipitates over the course of the reaction. In addition, it is interesting to show that the PP produced contains isotactic linkages. These results are in contrast to other late metal systems, where the other late metal systems are amorphous and atactic PP (54; Generally produces partially isotactic PP ([mm] = 0.41)) using the α-diimine Ni (II) system of Det et al. (63) or at lower temperatures Or introducing a syndiotactic chain. Increasing the monomer size to 1-hexene results in a loss of steric control.
Example 13

All manipulations of air and / or water sensitive compounds were performed under an inert atmosphere using standard glove box and Schlenk-Line techniques. Dichloromethane (CH ₂ Cl ₂ ) was distilled using CaH ₂ and 1-hexene was distilled using Na / K alloy. Toluene was purchased from Aldrich (anhydrous grade) and used as received. MAO (methylaluminoxane solution, 10% by weight in toluene) was purchased from Aldrich and dried under vacuum until a free flowing white powder was obtained. Ethylene (99.99%) and propylene (99.97%) were purchased from Mateson Trigas and purified by passing through an Agilent moisture and oxygen trap. Initiator 1 was synthesized as described above (57). Unless otherwise specified, reagents were purchased from Aldrich and used without further purification. The polymerization activity was calculated from the mass of the obtained product. At 135 ° C. in o-dichlorobenzene, the polymer was evaluated by GPC analysis in comparison to polystyrene standards (high temperature chromatograph, Pl-GPC 200 in the polymer laboratory). In a TA Instruments differential scanning calorimeter (model Q-20), using a temperature range of −70 to 180 ° C., melting point (T _m ) and glass transition temperature (T _g ) in 3 cycles at a rate of 10 ° C./min. Was measured.
Example 14

Ethylene polymerization: Toluene (40 mL) and solid MAO with [Al] / [Ni] = 250 (22 mg, 0.375 mmol) in the glove box of a 100 mL steel autoclave reactor equipped with an additional funnel. It was thrown to become. A stock solution of initiator 1 was prepared and 1.5 μmol of initiator 1 contained in about 1 mL of CH ₂ Cl ₂ was added to an additional funnel. In entry 8 of Table 8, 0.75 μmol initiator 1 contained in about 1 mL CH ₂ Cl ₂ was added to an additional funnel. [Al] / [Ni] = 250 (11 mg, 0.188 mmol) was maintained in this reaction. The reactor was sealed inside the glove box and an ethylene line was attached. An additional funnel was pre-pressurized with ethylene at 50 psi, the desired reaction pressure described above with ethylene. The reactor was pre-pressurized to (P _CH2H4 ) with ethylene and cooled to the appropriate temperature (T _rxn ). The polymerization was initiated by charging the initiator 1 solution, and ethylene was continuously fed into the reactor over the course of the reaction. The reaction temperature (T _rxn ) was controlled using a dry-ice / acetone bath and was ± 2 ° C. as monitored by an internal thermocouple. After a predetermined time, ethylene was discharged and methanol was added to cool the polymerization (entries 1-6). The polymer was precipitated with methanol, collected by filtration, washed successively with acidic methanol (10% HCl), methanol and acetone and dried under high vacuum to constant weight. The polymerization activity was calculated from the mass of the obtained product. In a reaction using triethylsilane (Et ₃ SiH) as a coolant (Table 7, entries 7 and 8, and Table 8), 1 mL of Et ₃ SiH contained in 2 ml of toluene was used as a starting material solution. Was added to an additional funnel following the introduction of. An additional funnel was pre-pressurized with ethylene at 50 psi, the desired reaction pressure (P _CH2H4 ) described above with ethylene, and the solution was _charged at the appropriate time under rapid stirring conditions.

Example 15

Living polymerization of propylene: In a glove box of a 300 mL steel autoclave reactor equipped with an additional funnel, toluene (100 mL) and solid MAO with [Al] / [Ni] = 250 (145 mg, 2.50 mmol). It was thrown to become. 10 μmol initiator 1 contained in about 1 mL CH ₂ Cl ₂ was added to the additional funnel. The reactor was sealed inside the glove box. The reactor was cooled in a dry-ice / acetone bath and 5 mL of propylene was transferred into the reactor. The reactor was brought to the appropriate reaction temperature (T _rxn ) and the polymerization was initiated by charging the initiator 1 solution under argon. The reaction temperature (T _rxn ) was controlled by a dry-ice / acetone bath and monitored by an internal thermocouple to be ± 2 ° C. To monitor the number average molecular weight (M _n ) and polydispersity (PDI) of the product over time; 5.0 mL aliquots in the polymerization solution under a stream of argon using a gas tight syringe, 20, 40, 60 and Collected at 90 minutes. The contents of the syringe were quickly cooled with methanol. Volatiles were removed under vacuum and the residue was washed successively with acidic methanol (10% HCl), methanol and acetone and dried under high vacuum. The remaining residue was dissolved in about 5 g of o-dichlorobenzene by heating the contents to 135 ° C. with stirring. Gel permeation chromatography (GPC) of this solution was used to obtain M _n and PDI for each polymer sample as shown in Table 9. The reaction at 120 minutes was cooled by charging methanol (5 mL) into an additional funnel and pouring the methanol directly into the stirring reaction mixture under argon. The polymer was precipitated with methanol, collected by filtration, washed successively with acidic methanol (10% HCl), methanol and acetone and dried to constant weight under high vacuum. The polymerization activity was calculated from the mass of the obtained product.

Example 16

Living polymerization of 1-hexene: Toluene (125 mL), 1-hexene and solid MAO in the glove box of a 300 mL steel autoclave reactor equipped with an additional funnel [Al] / [Ni] = 250 (181 mg, 3.13 mmol) was added. A stock solution of initiator 1 was prepared and 12.5 μmol of initiator 1 contained in about 1 mL of CH ₂ Cl ₂ was added to the additional funnel. The reactor was sealed inside the glove box and cooled to the appropriate reaction temperature (T _rxn ) in a dry-ice / acetone bath. Polymerization was initiated by charging a solution of initiator 1 under argon. The reaction temperature (T _rxn ) was controlled by a dry-ice / acetone bath and monitored by an internal thermocouple to be ± 2 ° C. To monitor the number average molecular weight (M _n ) and polydispersity (PDI) of the product over time; 5.0 mL aliquots in the polymerization solution under a stream of argon using a gas tight syringe, 20, 40, 60 and Collected at 90 minutes. The contents of the syringe were quickly cooled with methanol. Volatiles were removed under vacuum and the residue was washed successively with acidic methanol (10% HCl), methanol and acetone and dried under high vacuum. The remaining residue was dissolved in about 5 g of o-dichlorobenzene by heating the contents to 135 ° C. with stirring. Gel permeation chromatography (GPC) of this solution was used to obtain M _n and PDI for each polymer sample as shown in Table 10. The reaction at 120 minutes was cooled by charging methanol (5 mL) into an additional funnel and pouring the methanol directly into the stirring reaction mixture under argon. The polymer was precipitated with methanol and the precipitated polymer was collected by filtration, washed successively with acidic methanol (10% HCl), methanol and acetone and dried under high vacuum to a constant weight. The polymerization activity was calculated from the mass of the obtained product.

Although the present invention has been described with reference to preferred embodiments, modifications and variations can be utilized without departing from the principles and scope of the present invention, as will be readily appreciated by those having ordinary skill in the art. Getting is to be understood. Accordingly, such modifications can be practiced within the scope of the claims.

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Claims (27)

Organometallic composites that are initiators that allow polymerization and copolymerization of olefins into high molecular weight polymers according to the following formula (I):

here:
R, R ′, R ″ and R ′ ″ are each independently an achiral or chiral alkyl or aryl group with or without one or more functional groups;
M is Fe, Co, Ni, Pd or Pt;
X is an alkyl, hydrogen or halogen group; and
L is O, N—R ″ ″, S or ═CH ₂ , where R ″ ″ is an alkyl or aryl group.   The complex of claim 1, wherein R and R ′ are each alkyl, and R ″ and R ″ ″ are each aryl.   The complex according to claim 1, wherein L is O.   4. The complex of claim 3, wherein R and R 'are each alkyl, and R "and R" "are each aryl.   The complex according to claim 4, wherein R and R 'are each methyl.   5. The complex of claim 4, wherein R "and R" "are each 2,6-disubstituted aryl.   The complex is 2,4-bis (2,6-diisopropylphenylimino) pentan-3-one dibromonickel or 2,4-bis (2-isopropyl-6-methylphenylimino) pentane-3-onedibromonickel. The composite according to claim 4. A process for producing an organometallic complex that is an initiator comprising mixing a metal compound with a ligand of formula II:

Where R, R ′, R ″ and R ′ ″ are each independently an achiral or chiral alkyl or aryl group with or without one or more functional groups, and L is O , N—R ″ ″, S or ═CH ₂ , where R ″ ″ is an alkyl or aryl group.   9. The method of claim 8, wherein R and R 'are each alkyl and R "and R" "are each aryl.   The method of claim 8, wherein L is O.   11. The method of claim 10, wherein R and R 'are each alkyl, and R "and R" "are each aryl.   9. A process according to claim 8, wherein R "and R" "are 2,6-diisopropylphenyl or 2-isopropyl-6-methylphenyl, respectively.   The method according to claim 8, wherein the metal compound is a metal halide compound complex.   The method according to claim 13, wherein the metal compound is a (1,2-dimethoxyethane) dibromonickel complex. One or more olefins mixed with organic metal complex and cocatalyst, the a 1 or 2 or more polymerization processes for producing a polymer comprising olefin, organometallic complexes of formula (I) that has:

here,
R, R ′, R ″ and R ′ ″ are each independently an achiral or chiral alkyl or aryl group with or without one or more functional groups;
M is Fe, Co, Ni, Pd or Pt;
X is an alkyl, hydrogen or halogen group; and
L is O, N—R ″ ″, S or ═CH ₂ , where R ″ ″ is an alkyl or aryl group.   The polymerization method according to claim 15, wherein R and R ′ are each alkyl, and R ″ and R ″ ″ are each aryl.   The polymerization method according to claim 15, wherein L is O.   18. The polymerization method according to claim 17, wherein R and R 'are each alkyl, and R "and R" "are each aryl.   The complex is 2,4-bis (2,6-diisopropylphenylimino) pentan-3-one dibromonickel or 2,4-bis (2-isopropyl-6-methylphenylimino) pentane-3-onedibromonickel. The polymerization method according to claim 15. The one or more olefins are each independently: R ¹ CH═CH ₂ ; cyclopentene; styrene; norbornene; cyclopentene, styrene or norbornene substituted with one or more substituents; or the formula H ₂ C═ A polar olefin of CR ² X; wherein R ¹ is hydrogen, an alkyl group, or an alkyl group substituted with one or more functional groups; R ² is hydrogen, an alkyl group, an aryl group or an alkoxy group The polymerization method according to claim 15, wherein X is a polar group. X is: _{halogen; -CN; -C 6 H 5 N} ; -CONR 3 R 4; -OR 3; -COOR 3; -OCOR 3; -COR 3; -C 6 H 5 OR 3; or -C ₆ be H ₅ NR ³ R ^4; wherein, R ³ and R ^4, polymerization process of claim 20 are each independently hydrogen or an alkyl group.   The polymerization method according to claim 15, wherein a single olefin is polymerized.   The polymerization method according to claim 22, wherein the produced polymer is polyethylene or polypropylene.   The polymerization method according to claim 15, wherein two different olefins are polymerized.   The method of claim 15, wherein the polymer is polymerized by a living polymerization process.   26. The method of claim 25, wherein two different olefins are polymerized such that a block polymerization is produced. The polymerization method according to claim 15 , wherein the cocatalyst is an alkylaluminum, an aluminoxane, or a borate compound.

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